Water-insoluble disazo dyes



United States Patent 3,117,959 WATER-INSULUBLE DISAZO DYES JohannesDehnert, Ludwigshafen (Rhine), Germany, assignor to Badische Anilin- 8:Soda-Fabrilr Aktiengesellschaft, Ludwigshafen (Rhine), Germany NoDrawing. Filed July 20, 1961, Ser. No. 125,368

(Ilaims priority, application Germany July 30, 1%0 6 Claims. (Cl.269-155) This invention relates to new water-insoluble disazo dyes, theproduct of these disazo dyes by coupling 4- aminoazobenzenes with4-hydroxyquinolone derivatives, and the use of these dyes for dyeing andprinting textile materials, plane shapes, shaped articles and similarmaterials of high molecular weight synthetic substances.

In the dyeing and printing of textile materials, such as fibers,filaments, flock, woven and non-Woven textiles, plane shapes, such asfilms, sheets or plates, shaped articles, such as rods, tubes, balls orsimilar products of high molecular weight synthetic substances, such ascellulose esters, cellulose ethers, linear polyamides, linearpolyurethanes, polyacrylonitrile and copolymers of acrylonitrile withother monomers, such as vinyl acetate, vinylidene cyanide or vinylchloride, linear polyesters, such as polyethylene terephthalate orpolyhexahydroterephthalyl terephthalate (marketed under the name KODEL,a trade mark of Eastman Chemical Product Inc., Kingsport, Tennessee), itis of decisive importance that the dyes used should have not onlybrilliance, high color strength and good fastness to wet treatment andrubbing, but above all good fastness to light.

It is an object of this invention to provide dyes which fully satisfythese requirements.

Another object of this invention is to provide dyes which give onsynthetic linear polyesters dyeings and prints of outstanding allroundfastness, especially outstanding light fastness.

These and further objects are achieved by using the new dyes having thegeneral formula:

in which R denotes a hydrogen atom or a low molecular Weight,substituted or unsubstituted alkyl or aryl radical which may also becombined with the carbon atom in 8-position of the quinolone skeleton,and the benzene rings A, B and C may bear further substituents but nosulfonic or carboxylic acid groups.

Examples of substituents which may be contained in the benzene rings A,B and C are halogen atoms, alkyl, hydroxyalkyl, alkoxyalkyl, cyanoalkyl,carboxyalkyl-alkyl, carbonamidoalxyl, cyanoalkyl, alkoxy, hydroxyalkoxy,carboxylic acid amide, sulfonic acid amide, cyano, carboxylic acid esterand/ or nitro groups.

The valuable new dyes of this invention are obtained by coupling adiazotized 4-aminoaz0benzene free from sulfonic acid and carboxylic acidgroups with a 4-hydroxyquinolone-(2) of the general formula:

in which R has the meaning given above, and which may bear in the ring Afurther substituents, but no sulfonic acid or carboxylic acid groups.

Coupling is eiiected in the usual manner in water or in an organicsolvent or in a mixture of the two. Suitable organic solvents includealcohols, such as methanol or ethanol; glycois, such as ethylene glycolor diethylene glycol; glycol ethers, such as ethylene glycol monomethylether; N-methylpyrrolidone, pyridine or dimethylformamide. If couplingis effected in water or mixtures of water and organic solvents, it ispreferable to add dispersing agents to the coupling mixture.Polyoxyethylated sperm oil alcohols or their acid sulfuric acid estersin the form of their alkali salts or the sodium salts of the disulfonicacids of dinaphthylmethanes may for example be used as dispersingagents.

Examples of 4*am'moazobenzenes which may be used as diazo componentsare:

4-aminoazobenzene,

3 ,2-dimethyl-4-amino azobenzene, 2-methyl-5-methoxy-4-aminoazobenzene,2,S-dimethoxyl-aminobenzene, 4'-methoxy-4-aminoazobenzene,2-rnethyl-4-*nethoxy-4-aminoazobenzene,3,6,4'-trimethoxy-4-aminoazobenzene, 4-chloro-4-aminoazobenzene and4-aminoazobenzene-4'-sulfonic acid amide.

Examples of suitable coupling components are:

1-fi-methoxyethyl-7-trifiuoromethyl-4-hydroxyquinolone-(Z)1-tihydroxyethyl-6-chloro-4-hydroxyquinolone- (2)1-/5'-cyanoethyl-6-nitro-4-hydroxyquinolone-(2),1-[3-carboxymethyl-ethyl-6-bromo-4-hydroxyquinolone- (2)1-B-methoxy-ethyl-6-chloro-4-hydroxyquinolone-(2) and the quinolones ofthe following formulae:

Haj-CH C2 I II III The preparation of quinolone I fromtetrahydroquinoline and diethyl malonate is described in Berichte derDeutschen Chemischen Gesellschaft, vol. 25 (1892), p. 1194. Qinolone IIis accessible in an analogous manner from Z-methylindoline and diethylmalonate. Quinolone III is obtained by boiling a mixture ofZ-ethylaminonaphthalene, diethyl malonate and diphenyl ether for twohours. The other coupling components specified may be prepared accordingto the process described in US. Patent No. 2,529,924.

Dyes of the general formula:

have proved particularly suitable for dyeing and printing synthetic highmolecular weight organic substances, especially of linear syntheticpolyesters, such as polyethylene terephthalate. They are thereforepreferred for the said purpose. In the said formula, R denotes ahydrogen atom or a halogen atom, for example, a chlorine atom, R denotesa hydrogen atom or an alkyl group, for example a methyl group, R denotesa hydrogen atom, an alkyl group or an alkoxy group, for ex ample amethyl, ethyl, methoxy or ethoxy group, R denotes a hydrogen atom, analkyl group or an alkoxy group, for example a methyl, ethyl, methoxy orethoxy group, and X denotes one of the divalent radicals of theformulae:

R R5 I I I I I I a R5 at a r a, (DEL-OH: om-om and in which R denotes ahydrogen atom, a low molecular weight alkyl group, for example a methyl,ethyl, propyl or butyl group, a phenyl group, a hydroxyalkyl group, forexample a fi-hydroxyethyl, ,B-hydroxypropyl or 'y-hy droxypropyl group,a dihydroxyalkyl group, for example a Byy-dihydroxypmpyl group, analkoxyalkyl group, for example a ,B-methoxyethyl, B-ethoxyethyl or'y-methoxypropyl group, a cyano-alkyl group, for example a fi-cyanoethylor fl-cyanopropyl group, a carboxyalkyl-alkyl group, for example a,B-carboxymethylethyl, ,B-carboxyethyl-ethyl or B-carboxymethyl-propylgroup, or a carbonamido-alkyl group, for example a B-carbonamidoethyl orfi-carbonamido-propyl group, R denotes a hydrogen atom or an alkoxygroup, for example a methoxy or ethoxy group, R denotes a hydrogen atom,a trifluoromethyl or alkoxy group, for example a methoxy or propoxygroup, R denotes a hydrogen atom or halogen atom, for example a chlorineor bromine atom, or a nitro group, R denotes a hydrogen atom or ahalogen atom, for example a chlorine atom or a bromine atom, and Rdenotes a low molecular weight alkyl group, for example a methyl groupor an ethyl group.

The new dyes are suitable, especially in finely divided form, for thedyeing or printing of textile materials, such as fibers, flock,filaments, woven or non-woven textiles, or shaped articles of celluloseesters or cellulose ethers or synthetic fiber-forming substances, suchas linear polyamides or polyurethanes, polyacrylonitrile and copolymersof acrylonitrile, especially of synthetic linear polyesters, such aspolyethylene terephthalate or polyhexahydroterephthalylterephthalate.When dyeing the lastmentioned materials, it is preferable to add dyeingaccelerators (carriers) or to use temperatures above 100 C.(high-temperature dyeing).

Suitable carriers include 2-phenylphenol, biphenyl, trichlorobenzene,methylsalicylate, p-chlorophenyl ,8 hydroxyethyl ether and dimethylterephthalate.

The invention is illustrated by, but not limited to, the followingexamples. The parts specified in the examples are by weight. Parts byvolume bear the same relation to parts by weight as the liter to thekilogram under standard conditions. Percentages are by weight.

Example 1 19.7 parts of 4-aminoazobenzene is finely ground with 40 partsby volume of concentrated hydrocloric acid and, after standing forseveral hours, 200 parts of ice is added to the mixture and then,gradually, 30 parts by volume of a 23% aqueous sodium nitrite solution.The mix ture is stirred for two hours at 0 to 5 C. 50 parts by volume ofa 50% aqueous sodium acetate solution and then, while stirring, asolution of 19 parts of l-methyl 4-hydroxyquinolone-(2) in 220 parts byvolume of a 2% caustic soda solution are allowed to flow in slowly. Atthe same time, another 50 parts by volume of a 50% aqueous sodiumacetate solution is added in small portions. The yellow dye obtained isfiltered off, washed with water and dried. It dissolves in aqueousacetone or in dimethylformamide with a yellow color. 7 0.5 part of thisfinely divided disazo dye is added to a bath of 3000 parts of water and1.5 parts of the product obtained by adding on 80 moles of ethyleneoxide to 1 mole of sperm oil alcohol and sulfonating the product, and100 parts of polyethylene terephthalate film is dyed therein for minutesat boiling temperature.

The golden yellow dyeing obtained is characterized by high colorstrength, excellent thermal stability and very good wet and lightfastness properties.

The dyes of the following table are obtained in an analogous manner:

6 10 parts of this disazo dye is added as a finely divided powder to apaste of 360 parts of water, 600 parts Example No.

Shade of dyeing on polyethylene terephthalate CH3 CH3 0H orange.

red.

claret.

orange.

Example 6 The disazo solution obtained from 19.4 parts of 4aminoazobenzene as described in Example 1 is allowed to flow graduallyinto a solution of 24 parts of l-butyl- 4-hydroxyquinolone-(2) in 500parts by volume of dimethylformamide and then 200 parts by volume of a50% aqueous sodium acetate solution is slowly added. When coupling iscomplete, the yellow dye obtained is filtered 01f, washed with water anddried. It is obtained in the form of a yellow-brown powder whichdissolves in 80% acetone or in dimethylformamide with a reddish yellowcolor.

of a natural gum thickening and 25 parts of Z-phenylphenol and a fabricof polyethylene terephthalate is printed with this paste. The printedfabric is dried and treated for 15 minutes with steam at 1.5 atmospheresgage. The reddish yellow print obtained exhibits excellent thermalstability and moreover has very good wet and light fastness. The sameresult is achieved by using diphenyl, trichlorobenzene, methylsalicylate, p-chlorophenyl-B-hydroethyl ether or dimethylterephthalateas carriers instead of 2-phenylphenol.

The following dyes are obtained in an analogous man- 50 ner:

Example N0. Shade of dyeing on polyethylene terephthalate I OH I 7 N=-N=N reddish-yellow l HzC CH Example N0.

Shade of dyeing on polyethylene terephthalate CaH7 OH: OCH; (RH-OH CHzOHyellow.

reddish-yellow.

Example No. Shade of dyeing o polyethylene terephthalate (IJH 18 O N CHI CHPOHPO C2 5 (')H 19 G =NN=N Do.

fi CHqCH2COOC2Hs CH2CH2OH (IJH 21 O- N CFs I CHzOHzOCH3 C| H C1 ICH2CH2CH2OH 01H hi CHzCH2-CN (IJH CHzCH2COOCH OHzCH O CH;

Example 26 HOW w in 1000 parts by volume of a 0.5% aqueous caustic sodasolution, which also contains 10 parts of the disodium salt of1,1'-dinaphthylmethane-2,2'-disulfonic acid as dispersing agent, isallowed to flow in slowly. At the same time, another 50 parts by volumeof a 50% aqueous sodium acetate solution is gradually added. TheWater-insoluble dye thus obtained is, after isolation and drying, anorange powder which dissolves in dimethylformamide to give a similarcolor.

parts of polyethylene terephthalate fiber is dyed for 60 minutes at C.in a pressure apparatus in a bath of 2000 parts of Water, 0.6 part ofthe said finely divided disazo dye and 2 parts of the product obtained 7by adding on 80 moles of ethylene oxide to 1 mole of 1 1 sperm oilalcohol and subsequent sulfonation. A11 orange dyeing is obtained havingexcellent thermal stability and very good Wet and light fastnessproperties.

I claim: 7 1. A water-insoluble dye of the formula (|)H /C\ N=N- N=N o Xo II in which:

X denotes a divalent radical selected from the class consisting of theradicals of the formulae:

I I I a Re a a B5 OHz-CH CH-C1H2 R denotes a member selected from theclass consisting of methyl, ethyl, propyl, butyl, phenyl,IS-hydroxyethyl, 3 hydroxypropyl, 7 hydroxypropyl, 8, dihydroxypropyl,fl-methoxyethyl, B-ethoxy-ethyl, B-cyanoethyl, fi-carboxymethyl-ethyl,fi-carboxyethyl-ethyl, and B-carboamidoethyl;

R denotes a member selected from the class consisting of hydrogen andmethoxy;

R denotes a member selected from the class consisting of hydrogen,methyl and trifluoromethyl;

R denotes a member selected from the class consisting of hydrogen,chlorine, bromine and nitro; and

R denotes a member selected from the class consisting of hyrogen andchlorine.

2. A Water-insoluble disazo dye of the formula:

lower alkyl 3. The dye of the formula:

4. The dye of the formula:

5. The dye of the formula:

6. The dye of the formula:

References Cited in the file of this patent UNITED STATES PATENTS UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3 ll7 959January 14L, 1964 Johannes Dehnert It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected belo*.

Column 2, lines 5 to 11, the formula should appear as shown belowinstead of as in the patent:

(SEAIJ Signed and sealed this 21st day of July 1964o Attest:

ESTON G. JOHNSON EDWARD J. BRENNER Ittesting Officer Commissioner ofPatents

1. A WATER-INSOLUBLE DYE OF THE FORMULA